EP0455119A2 - Procédé pour la préparation de la canthaxanthine et de l'astaxanthine - Google Patents

Procédé pour la préparation de la canthaxanthine et de l'astaxanthine Download PDF

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Publication number
EP0455119A2
EP0455119A2 EP91106567A EP91106567A EP0455119A2 EP 0455119 A2 EP0455119 A2 EP 0455119A2 EP 91106567 A EP91106567 A EP 91106567A EP 91106567 A EP91106567 A EP 91106567A EP 0455119 A2 EP0455119 A2 EP 0455119A2
Authority
EP
European Patent Office
Prior art keywords
general formula
formula
reacted
canthaxanthin
triphenylphosphine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP91106567A
Other languages
German (de)
English (en)
Other versions
EP0455119A3 (en
Inventor
Hansgeorg Dr. Ernst
Joachim Dr. Paust
Werner Dr. Hoffmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0455119A2 publication Critical patent/EP0455119A2/fr
Publication of EP0455119A3 publication Critical patent/EP0455119A3/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
    • C07C403/12—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5435—Cycloaliphatic phosphonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the invention relates to a new process for the preparation of the sought-after carotenoids canthaxanthin (Ia) and astaxanthin (Ib).
  • the halides of the formula below are used as C15-phosphonium salts, the bromide in particular being used as the anion of the phosphonium salt.
  • the phosphonium salts suitable according to the above-described synthesis principle C15 + C10 + C1 nach as C15 building blocks for canthaxanthin or astaxanthin are obtained by reacting the corresponding allyl bromides of the formula made with triphenylphosphine.
  • butylene oxide In the further processing of the allyl bromide, butylene oxide must also be added several times to trap acid traces.
  • the tertiary alcohol of the formula IIa is converted by treatment with phosphorus tribromide in an inert organic solvent into the corresponding allyl bromide, from which the corresponding phosphonium salt is obtained by reaction with triphenylphosphine (DE-OS 2 801 908) .
  • triphenylphosphine DE-OS 2 801 908
  • a considerable excess ⁇ 3 equivalents
  • the triphenylphosphonium bromide can also be prepared directly from the tertiary alcohol of the formula IIa by reaction with triphenylphosphine hydrobromide (cf. DE-OS 2 801 908).
  • this reagent must be prepared in an additional step from triphenylphosphine and HBr and must also be used in a considerable excess.
  • the invention also relates to the new intermediates of the formulas III and IV which enable the advantageous new process.
  • the reaction of the tertiary alcohols of the formula II with trifluoroacetic acid is generally carried out in an inert organic solvent, such as methylene chloride, 1,2-dichloroethane or ethyl acetate, at temperatures from about 0 ° C. to + 50 ° C., preferably 10-30 ° C., in particular at room temperature. Only 1.0-1.05 equivalents of trifluoroacetic acid, based on the alcohols of the formula II, are required here.
  • the new trifluoroacetates of the formula III are obtained in a smooth reaction and in good yields, without the secondary hydroxyl group of IIIb being esterified and without the risk that the ⁇ -ketol is rearranged into the diosphenol.
  • the crude trifluoroacetates of the formula III can be further processed directly to the phosphonium salts of the formula IV, for example by heating with a triarylphosphine, in particular triphenylphosphine, in an inert organic solvent such as toluene, ethyl acetate or methylene chloride.
  • a triarylphosphine in particular triphenylphosphine
  • an inert organic solvent such as toluene, ethyl acetate or methylene chloride.
  • the triphenylphosphine is generally used in amounts of 1.0 to 1.2 moles per mole of trifluoroacetate of the formula III.
  • the reaction is generally carried out at from room temperature to the reflux temperature of the solvent used, preferably at from about 50 to 100.degree.
  • the reaction time is, for example, about 15 to 30 minutes when the reaction is carried out without a solvent in the temperature range from 80 to 100 ° C.
  • the crude phosphonium salt of the formula IV obtained in this way can be purified by precipitation from a suitable organic solvent, such as methyl tert-butyl ether (MTB) or diisopropyl ether.
  • a suitable organic solvent such as methyl tert-butyl ether (MTB) or diisopropyl ether.
  • carotenoids canthaxanthin Ia are obtained from the phosphonium salts of the formula IVa or IVb by reaction with the C10 dialdehyde 2,7-dimethyl-2,4,6-octatriene-1,8-dial under the reaction conditions typical of such Wittig condensations or astaxanthin Ib in good yields.
  • the phosphonium salt IVb was obtained in the form of colorless crystals by redissolving in ethyl acetate and dropwise adding MTB. Mp .: 147-148 ° C, calculated fluorine value: 9.4%, analytically determined fluorine value: 9.5%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP19910106567 1990-05-03 1991-04-24 Process for the preparation of canthaxanthin and astaxanthin Withdrawn EP0455119A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4014203A DE4014203A1 (de) 1990-05-03 1990-05-03 Verfahren zur herstellung von canthaxanthin und astaxanthin
DE4014203 1990-05-03

Publications (2)

Publication Number Publication Date
EP0455119A2 true EP0455119A2 (fr) 1991-11-06
EP0455119A3 EP0455119A3 (en) 1992-04-15

Family

ID=6405641

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910106567 Withdrawn EP0455119A3 (en) 1990-05-03 1991-04-24 Process for the preparation of canthaxanthin and astaxanthin

Country Status (4)

Country Link
US (1) US5210314A (fr)
EP (1) EP0455119A3 (fr)
JP (1) JPH04225933A (fr)
DE (1) DE4014203A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994002881A1 (fr) * 1992-07-21 1994-02-03 Basf Aktiengesellschaft Polyenes a proprietes optiques non lineaires
EP0633258A1 (fr) * 1993-07-05 1995-01-11 BASF Aktiengesellschaft Procédé amélioré de production d'astaxantin, nouveaux produits intermédiares et procédé de leur préparation
CN1045004C (zh) * 1994-03-25 1999-09-08 武田药品工业株式会社 制备胡萝卜素类化合物的方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19509955A1 (de) * 1995-03-18 1996-09-19 Basf Ag Verfahren zur Herstellung von Astaxanthin
DE59912915D1 (de) * 1998-08-05 2006-01-19 Dsm Ip Assets Bv Herstellung von 4,4'-Diketo-carotinoiden
CL2008001699A1 (es) 2008-06-09 2010-02-05 Univ Chile Secuencia de adn que codifica enzima con actividad citocromo p450 reductasa de x. dendrorhous; secuencia de polipeptido codificada; vector o plasmido; celula hesped; proceso de produccion de polipeptido; proceso de produccion de astaxantina desde beta-caroteno; composiciones, productos y/o formulaciones.

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3006939A (en) * 1957-01-17 1961-10-31 Basf Ag Production of compounds of the betacyclogeranylidene series
CH623304A5 (fr) * 1975-11-30 1981-05-29 Hoffmann La Roche
US4088689A (en) * 1976-09-15 1978-05-09 Hoffmann-La Roche Inc. Cyclohexenone phosphonium salts
US4098827A (en) * 1977-01-17 1978-07-04 Hoffmann-La Roche Inc. 1-(2,6,6-Trimethyl-3-hydroxy-1-cyclohexen-1-yl)-3-methyl-penta-1,4-diene[or 1-yn-4-EN]-3-ols
EP0005749B1 (fr) * 1978-06-02 1983-03-30 F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft Dérivés de la cyclohexéne, procédé de leur préparation, ainsi que leur utilisation
DE2964401D1 (en) * 1978-06-02 1983-02-03 Hoffmann La Roche Process for the preparation of cyclohexenyl derivatives, and intermediates produced in the synthesis
EP0101597B1 (fr) * 1982-08-20 1988-06-22 F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft Procédé pour la préparation de l'astaxanthine ainsi que les produits intermédiaires dans la synthèse de l'astaxanthine

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994002881A1 (fr) * 1992-07-21 1994-02-03 Basf Aktiengesellschaft Polyenes a proprietes optiques non lineaires
EP0633258A1 (fr) * 1993-07-05 1995-01-11 BASF Aktiengesellschaft Procédé amélioré de production d'astaxantin, nouveaux produits intermédiares et procédé de leur préparation
CN1052001C (zh) * 1993-07-05 2000-05-03 Basf公司 虾青素的制备、制备它的新中间体
CN1045004C (zh) * 1994-03-25 1999-09-08 武田药品工业株式会社 制备胡萝卜素类化合物的方法

Also Published As

Publication number Publication date
DE4014203A1 (de) 1991-11-07
JPH04225933A (ja) 1992-08-14
EP0455119A3 (en) 1992-04-15
US5210314A (en) 1993-05-11

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